JP6091310B2 - Method for producing butadiene - Google Patents

Description

  The present invention relates to a method for producing butadiene using acetaldehyde and alcohol as raw materials.

  The main source of butadiene is an extract from a 4 carbon distillate in a naphtha pyrolysis furnace (cracker), but naphtha pyrolysis is primarily intended for the production of ethylene and propylene, and butadiene is a byproduct. It is only treated as. In addition, demand for butadiene is expected to increase in emerging countries, but since the production volume is not sufficient, development of a new butadiene manufacturing method is required.

  A method for producing butadiene using acetaldehyde and alcohol as raw materials has been known for a long time, and non-patent document 1 (Catalysis Science and Technology 1 (2011) pp. 267-272) estimates a reaction mechanism as described below. Yes. Patent Document 1 (US Pat. No. 2,421,361) discloses an example in which an oxide of zirconium, tantalum or niobium is used as a catalyst. Patent Document 2 (US Pat. No. 2,524,848) discloses the use of tantalum oxide supported on silica as a catalyst. However, these methods still have problems in practical use because of the low selectivity of butadiene.

US Pat. No. 2,421,361 US Pat. No. 2,524,848

Catalysis Science and Technology 1 (2011) pp. 267-272

  An object of the present invention is to provide a method for producing butadiene with high selectivity, using acetaldehyde and alcohol as raw materials.

  As a result of various studies, the present inventors have found that as a catalyst for producing butadiene from acetaldehyde and alcohol, at least one metal B selected from the group consisting of Groups 1 to 3 in the periodic table in addition to conventional tantalum oxide and the like. The present inventors have found that the above-mentioned problems can be solved by using the oxides together, and have completed the present invention. That is, the present invention relates to the following [1] to [6].

（Ｒ_１およびＲ_２は、水素原子または炭素数１〜２０の脂肪族炭化水素基であり、同じであっても異なっていてもよい。）
［２］
金属Ｂがナトリウム、バリウム、ランタン、およびイットリウムから選ばれる少なくとも１種である［１］に記載のブタジエンの製造方法。
［３］
金属Ａがジルコニウム、ハフニウム、およびタンタルから選ばれる少なくとも１種である［１］または［２］のいずれかに記載のブタジエンの製造方法。
［４］
触媒が成分Ａおよび成分Ｂが担体に担持されたものである［１］〜［３］のいずれかに記載のブタジエンの製造方法。
［５］
一般式（Ｉ）のＲ_１が水素原子、Ｒ_２が炭素数１〜６のアルキル基である［１］〜［４］のいずれかに記載のブタジエンの製造方法。
［６］
一般式（Ｉ）で示されるアルコールがエタノールである［１］〜［４］のいずれかに記載のブタジエンの製造方法。 [1]
A method for producing butadiene using acetaldehyde and an alcohol represented by the general formula (I) as a raw material, wherein at least one metal A oxide selected from the group consisting of groups 4 and 5 of the periodic table ( A method for producing butadiene, comprising using a catalyst containing component A) and at least one oxide of metal B selected from the group consisting of Groups 1 to 3 in the periodic table (component B).

(R ₁ and R ₂ is an aliphatic hydrocarbon group hydrogen atom or a C 1-20, it may be different even for the same.)
[2]
The method for producing butadiene according to [1], wherein the metal B is at least one selected from sodium, barium, lanthanum, and yttrium.
[3]
The method for producing butadiene according to any one of [1] or [2], wherein the metal A is at least one selected from zirconium, hafnium, and tantalum.
[4]
The method for producing butadiene according to any one of [1] to [3], wherein the catalyst is one in which component A and component B are supported on a carrier.
[5]
The method for producing butadiene according to any one of [1] to [4], wherein R _{1 in the} general formula (I) is a hydrogen atom, and R ₂ is an alkyl group having 1 to 6 carbon atoms.
[6]
The method for producing butadiene according to any one of [1] to [4], wherein the alcohol represented by the general formula (I) is ethanol.

  According to the present invention, butadiene can be produced with high selectivity using acetaldehyde and alcohol as raw materials.

（Ｒ_１およびＲ_２は、水素原子または炭素数１〜２０の炭化水素基であり、同じであっても異なっていてもよい。） The present invention is a method for producing butadiene using a reaction in which butadiene, an aldehyde or a ketone and two molecules of water are formed from two molecules of acetaldehyde and a primary or secondary alcohol as shown in Formula 1. According to Non-Patent Document 1, the presumed reaction mechanism is that two molecules of acetaldehyde are dehydrated after aldol condensation and converted to crotonaldehyde, which becomes crotyl alcohol by Merwine-Pondruf-Burley reduction (MPV reduction) with alcohol. Further, dehydration produces butadiene.

(R ₁ and R ₂ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may be different even for the same.)

  When ethanol is used as the alcohol, the ethanol is the same as acetaldehyde, that is, the raw material compound according to the formula (1), and as a result, the product is only butadiene and water. For this reason, the separation process of a product becomes simple and is more preferable.

  In order to improve the butadiene selectivity, it is important to suppress generation of olefins and / or ethers due to dehydration of alcohol, which is a side reaction, and formation of high molecular weight products from acetaldehyde.

（Ｒ_１およびＲ_２は、水素原子または炭素数１〜２０の脂肪族炭化水素基であり、同じであっても異なっていてもよい。） (Reaction form)

(R ₁ and R ₂ is an aliphatic hydrocarbon group hydrogen atom or a C 1-20, it may be different even for the same.)

In the alcohol represented by the general formula (I), R ₁ and R ₂ are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Further, R ₁ and R ₂ are preferably alkyl groups having 1 to 6 carbon atoms from the viewpoint of easy handling. Moreover, the primary alcohol whose R < ₁ > is a hydrogen atom is preferable. More preferably, R ₁ is a hydrogen atom, and R ₂ is an alkyl group having 1 to 6 carbon atoms.

  Examples of the alcohol represented by the general formula (I) include methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, i-butanol, crotyl alcohol and the like. Particularly preferred is ethanol in which the main product in formula (1) is only butadiene and water.

  As a raw material compound in the method for producing butadiene of the present invention, acetaldehyde and an alcohol represented by the general formula (I) are essential components, but other aldehydes may be used together. Examples of aldehydes other than acetaldehyde include crotonaldehyde and butyraldehyde having the same carbon number as butadiene which is the target compound.

  The ratio of the alcohol represented by the general formula (I) to acetaldehyde and optionally aldehydes other than acetaldehyde is preferably alcohol: aldehyde = 0.5: 1 to 10: 1 (molar ratio). More preferably, it is -5: 1 (molar ratio), and it is especially preferable that it is 1.5: 1-3: 1 (molar ratio).

  The reaction temperature suitable for the method for producing butadiene of the present invention is in the range of 100 ° C to 700 ° C. Preferably it is 250 to 600 degreeC, More preferably, it is 300 to 450 degreeC.

  Moreover, the pressure at the time of reaction may be normal pressure, under pressure or under reduced pressure, more preferably below normal pressure.

  The reaction format may be any of a batch system, a continuous system, a fixed bed, a moving bed, a fluidized bed, or a slurry bed.

  Although the present invention can be carried out using only the raw material compound, it can also be reacted by mixing an inert gas such as nitrogen or helium with the raw material compound and bringing it into contact with the catalyst. Water can be mixed with the raw material compound to promote the initiation and / or progress of the reaction.

  From the reaction product thus obtained, butadiene can be taken out by a commonly used separation and purification method. For example, butadiene can be taken out using rectification, extraction, adsorption, or the like.

(catalyst)
The catalyst that can be used in the method for producing butadiene of the present invention is at least one metal A selected from the group consisting of groups 4 and 5 in the group 18 element periodic table recommended by IUPAC in 1989. Examples thereof include a catalyst containing an oxide (component A) and an oxide (component B) of at least one metal B selected from the group consisting of Groups 1 to 3. Zirconium, hafnium, and tantalum are preferable as the metal A, and the component A that is an oxide thereof is preferably zirconium oxide, hafnium oxide, and tantalum oxide. The metal B is preferably sodium, barium, lanthanum and yttrium, and the component B which is an oxide thereof is preferably sodium oxide, barium oxide, lanthanum oxide and yttrium oxide.

  The specific action of the catalyst is unknown and is not desired to be bound by any theory, but can be estimated as follows. It is known that component A is active in the production of butadiene using acetaldehyde and alcohol as raw materials, but by adding component B thereto, the acid point of the raw materials and / or intermediate products is controlled to cause side reactions. As a result, the selectivity of butadiene can be improved.

  The catalyst used for this invention should just contain the component A and the component B, when using for manufacture of a butadiene. As precursor compounds of these components, any compound can be used without particular limitation as long as it becomes an oxide before being used for the production of butadiene. For example, inorganic salts such as nitrates, hydrochlorides, phosphates, sulfates, alcoholates such as ethoxides, propoxides, butoxides, etc. can be mentioned as catalyst precursor compounds. These can be used after being converted into oxides by heating, baking or the like.

  The firing temperature is 100 ° C to 900 ° C, preferably 300 ° C to 800 ° C, and more preferably 400 ° C to 700 ° C. Calcination can be performed in any atmosphere in air and an inert gas such as nitrogen or helium. Further, in the case of a catalyst precursor compound that can be converted to an oxide at a reaction temperature or lower, it can be used as it is as a catalyst layer.

  The catalyst can be used in any shape such as powder, granule, sphere, pellet and the like. It can also be used after drying and firing.

  The ratio of component A to component B is preferably 0.01 to 10 in terms of atomic ratio of metal contained in each component [(metal B in component B) / (metal A in component A)], 0.05 to 5 is more preferable, and 0.1 to 2 is still more preferable. If the loading amount is small, the effect is small, and if it is too large, the productivity may decrease.

  It is also possible to use the catalyst and / or catalyst precursor compound supported on a carrier as necessary. These carriers are not particularly limited as long as they are stable compounds in the heating zone. Examples of these compounds include alumina, silica, zeolite, magnesia, titania, zirconia, graphite, activated carbon, carbon fiber and the like.

  When the catalyst is supported on a support and used, the catalyst precursor compounds of component A and component B are dissolved together or separately in a soluble solvent such as ethanol, acetone, dichloromethane, chloroform, etc. After impregnation, the solvent can be removed if necessary, and the catalyst precursor compounds of component A and component B can be converted to oxides by heating, baking, or the like.

  The amount of component A supported on the carrier is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass with respect to the total mass of component A, component B and the carrier. 1 mass%-4 mass% are still more preferable. If the supported amount is small, the productivity is low, and if it is too large, the catalyst cost is high, which is not practical.

  The amount of component B supported is preferably 0.01 to 10 in terms of the atomic ratio of metal contained in each of component A and component B [(metal B in component B) / (metal A in component A)]. 05-5 are more preferable, and 0.1-2 are still more preferable. If the loading amount is small, the effect is small, and if it is too large, the productivity may decrease.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following example.

The calculation of the selectivity and yield of butadiene was determined by the following formula.

(Production gas analysis method)
The amount of each component in the gas after the reaction is contained in the liquid component and the gas component by cooling the gas after the reaction to room temperature, dividing it into a condensed liquid component and the remaining gas component, and analyzing each by gas chromatography. The total was determined. The analysis conditions are as follows.

Liquid component GC device: GC-14B manufactured by Shimadzu Corporation
Column: Capillary column TC-1 (length 60 m × inner diameter 0.25 mm × film thickness 1 μm)
Carrier gas: Helium Column temperature: 40 ° C., 6 minutes → Temperature increase 5 ° C./min→200° C., 2 minutes Detector: FID

Gas component 1 [analytical components: acetaldehyde, ethanol]
GC device: GC-14B manufactured by Shimadzu Corporation
Column: Packed column PEG-1540 (length 5 m)
Carrier gas: Helium Column temperature: 40 ° C, constant Detector: FID

Gas component 2 [analysis component: hydrocarbon (C1-C4)]
GC device: Agilent-7890A manufactured by Agilent Technologies, Inc.
Column: Capillary column HP-AL / S (length 25 m × inner diameter 0.32 mm × film thickness 8 μm)
Carrier gas: Helium Column temperature: 60 ° C, constant Detector: FID

Gas component 3 [analytical component: nitrogen]
GC device: Agilent-7890A manufactured by Agilent Technologies, Inc.
Column: Packed column molecular sieve 5A (length 5m)
Carrier gas: helium Column temperature: 60 ° C, constant Detector: TCD

Example 1
0.81 g of tantalum ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) in a glove box, and 50 mL of silica (CariACT Q-10; manufactured by Fuji Silysia Chemical Co., Ltd.) (22 g) was completely absorbed. Ethanol was removed by an evaporator and further dried at 100 ° C. overnight to obtain a tantalum precursor compound-supporting silica. 0.047 g of sodium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in water and completely absorbed in tantalum precursor compound-supported silica. After drying at 100 ° C. overnight, calcination was performed in air at 550 ° C. for 4 hours to obtain a tantalum oxide / sodium oxide-supported silica catalyst.

  10 mL of the obtained catalyst was charged into a flow reactor, the reaction temperature was 400 ° C., the pressure was atmospheric pressure, ethanol: acetaldehyde: water: nitrogen gas = 4: 2: 0.4: 3.6 L / H (0 ° C., 1 atmosphere) Butadiene was obtained in a yield of 22.1% and a selectivity of 66.5%. The selectivity of ethylene and diethyl ether were 6.3% and 6.8%, respectively.

(Examples 2 to 6)
As shown in Table 1, catalysts were prepared in the same manner as in Example 1, except that the type and ratio of component B (component B precursor) were changed. The same reaction as in Example 1 was performed using each of these catalysts. The results are shown in Table 1.

(Comparative Example 1)
A catalyst was prepared in the same manner as in Example 1 except that Component B was not supported. That is, 0.81 g of tantalum ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) in a glove box, and silica (CARIACT Q-10; manufactured by Fuji Silysia Chemical Co., Ltd.) was dissolved. ) The whole amount was absorbed in 50 mL. Ethanol was removed by an evaporator, and further dried at 100 ° C. overnight. Further, it was calcined in the air at 550 ° C. for 4 hours to obtain a tantalum oxide-supported silica catalyst.

  As a result of reacting in the same manner as in Example 1, butadiene was obtained with a yield of 25.9% and a selectivity of 58.5%. The selectivity of ethylene and diethyl ether were 11.1% and 10.1%, respectively.

( Reference Example 7)
In a glove box, 1.25 g of zirconium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved in 50 mL of silica (CARIACT Q-10; manufactured by Fuji Silysia Chemical Co., Ltd.). All was absorbed. Ethanol was removed by an evaporator and further dried at 100 ° C. overnight to obtain a zirconium precursor compound-supporting silica. 0.28 g of barium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in water and completely absorbed in the zirconium precursor compound-supported silica. After drying at 100 ° C. overnight, calcination was performed in air at 550 ° C. for 4 hours to obtain a zirconium oxide / barium oxide supported silica catalyst.

  10 mL of the obtained catalyst was charged into a flow reactor, the reaction temperature was 400 ° C., the pressure was atmospheric pressure, ethanol: acetaldehyde: water: nitrogen gas = 4: 2: 0.4: 3.6 L / H (0 ° C., 1 atmosphere) Butadiene was obtained in a yield of 22.3% and a selectivity of 54.2%. The selectivity for ethylene and diethyl ether were 1.6% and 0.7%, respectively.

(Comparative Example 2)
A catalyst was prepared in the same manner as in Reference Example 7 except that Component B was not supported, and a zirconium oxide-supported silica catalyst was obtained. As a result of reacting in the same manner as in Example 1, butadiene was obtained in a yield of 30.3% and a selectivity of 50.9%. The selectivity of ethylene and diethyl ether was 8.7% and 6.5%, respectively.

  In this way, at least one metal oxide selected from the group consisting of Group 1 to 3 is added to at least one metal oxide selected from the group consisting of Group 4 and Group 5, and the raw materials and / or By controlling the acid point of the intermediate product, by-products were reduced and butadiene selectivity was successfully improved. In addition, since unreacted raw materials can be recovered and recycled, it is important to improve the basic unit that the butadiene selectivity is high even if the yield is low.

Claims (4)

Raw material The method for producing butadiene with an alcohol represented by acetaldehyde and the general formula (I), tantalum oxide as metals A (components A), sodium, barium, lanthanum, and the group consisting of yttrium A method for producing butadiene, comprising using a catalyst comprising at least one metal B oxide (component B) selected from :

(R ₁ and R ₂ is an aliphatic hydrocarbon group hydrogen atom or a C 1-20, it may be different even for the same.) The method for producing butadiene according to claim 1, wherein the catalyst is one in which component A and component B are supported on a carrier. Method for producing butadiene according to claim 1 or 2 R ₁ is a hydrogen atom, R ₂ is an alkyl group having 1 to 6 carbon atoms in the general formula (I). The method for producing butadiene according to claim 1 or 2, wherein the alcohol represented by the general formula (I) is ethanol.